WO2013150931A1 - Procédé de traitement du graphène, procédé de production de nanorubans de graphène, et nanorubans de graphène ainsi obtenus - Google Patents

Procédé de traitement du graphène, procédé de production de nanorubans de graphène, et nanorubans de graphène ainsi obtenus Download PDF

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WO2013150931A1
WO2013150931A1 PCT/JP2013/058909 JP2013058909W WO2013150931A1 WO 2013150931 A1 WO2013150931 A1 WO 2013150931A1 JP 2013058909 W JP2013058909 W JP 2013058909W WO 2013150931 A1 WO2013150931 A1 WO 2013150931A1
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Prior art keywords
graphene
ion beam
cluster
clusters
water molecules
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PCT/JP2013/058909
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English (en)
Japanese (ja)
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貴士 松本
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東京エレクトロン株式会社
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Priority to KR1020147026445A priority Critical patent/KR20150006417A/ko
Priority to US14/390,402 priority patent/US20150179451A1/en
Publication of WO2013150931A1 publication Critical patent/WO2013150931A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/0405—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising semiconducting carbon, e.g. diamond, diamond-like carbon
    • H01L21/042—Changing their shape, e.g. forming recesses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/081—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing particle radiation or gamma-radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
    • H01L29/1606—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/06—Graphene nanoribbons

Definitions

  • the present invention relates to a graphene processing method useful as a material for various electronic components, a graphene nanoribbon manufacturing method, and a graphene nanoribbon obtained by this method.
  • Graphene has a structure in which carbon atoms are regularly arranged in a hexagonal shape on a plane, and has extremely high electrical conductivity. Graphene is attracting attention as a next-generation high-frequency device material because it has an electron mobility of 200,000 cm 2 / Vs and an excellent physical property of 100 times that of silicon (for example, Patent Document 1; Japan). (Japanese Unexamined Patent Publication No. 2008-205272, Patent Document 2; Japanese Unexamined Patent Publication No. 2011-114299, and Patent Document 3; Japanese Patent No. 46669957). Graphene is also expected to be applied to spintronic devices because not only electrons but also spin can be ballistically transported.
  • Graphene having such characteristics is a zero-gap semiconductor and cannot be turned off as it is.
  • graphene has a band gap that is inversely proportional to the width of the nano ribbon structure having a line width of 100 nm or less.
  • the edge shape of graphene is known to be zigzag edge (cis polyacetylene-like structure) and armchair edge (transpolyacetylene-like structure), and graphene nanoribbon has a large band gap unless the edge is armchair edge Does not occur.
  • Non-Patent Document 1 “NANOSCALE PATTERNING OF GRAPHENUS USING AFM LOCAL ANODIC OXIDATION”, K. YOSHIDA. , S.MASUBUCHI, M.ONO, K.HIRAKAWA, T.MACHIDA, Technical Digest. International Symposium on Graphology Devices: Technology, Physics8, Physics8, Physics.
  • Non-Patent Document 2 “Evaluation and processing of graphene on a solid substrate with a controlled structure”, Toshiro Kanno, Takahiro Tsukamoto, Journal of Japanese Society for Crystal Growth 37 (3), 207-213, 2010
  • the present invention provides a graphene processing method, a graphene nanoribbon manufacturing method, and a graphene nanoribbon for etching without damaging the graphene.
  • the graphene processing method according to the present invention uses a gas cluster ion beam apparatus to perform etching by irradiating graphene with an ion beam formed by ionizing water molecules or clusters in which water molecules are aggregated.
  • the edge shape is processed from the sheet-like graphene into an armchair-type graphene nanoribbon.
  • the method for producing a graphene nanoribbon according to the present invention uses a gas cluster ion beam apparatus to irradiate a sheet-like graphene with an ion beam formed by ionizing water molecules or clusters in which water molecules are aggregated, thereby forming an edge shape. Manufactures graphene nanoribbons at the end of armchairs.
  • the graphene nanoribbon according to the present invention has an edge shape at the end of an armchair obtained by irradiating a sheet-like graphene with an ion beam formed by ionizing water molecules or clusters in which water molecules are aggregated.
  • a graphene having a nanoribbon structure can be processed without damaging graphene by irradiating water molecules or cluster ions of water molecules using a gas cluster ion beam apparatus.
  • FIG. 1 is a schematic view of a gas cluster ion beam apparatus that can be preferably used in a graphene processing method according to an embodiment of the present invention.
  • the gas cluster ion beam apparatus 100 includes a vacuum vessel 1, and the vacuum vessel 1 includes a cluster generation unit 10 and an irradiation unit 20 separated by a partition wall 1a.
  • the irradiation unit 20 accommodates a substrate S on which a sheet-like graphene is formed on the surface that is the object to be processed.
  • An exhaust device 11 having a vacuum pump (not shown) or the like is connected to the cluster generation unit 10 through an exhaust port 10a so that the inside can be evacuated.
  • a nozzle 12 for introducing water vapor (H 2 O), which is a gas for generating a gas cluster, is disposed in the cluster generation unit 10.
  • a partition 1 a that separates the cluster generation unit 10 and the irradiation unit 20 is provided with a skimmer 13 having a hole through which the H 2 O cluster introduced from the nozzle 12 passes.
  • the skimmer 13 has a function of separating gas molecules not forming a cluster from the cluster beam. Although illustration is omitted, the nozzle 12 and the skimmer 13 are grounded, and their potential is 0V.
  • the irradiating unit 20 is connected to an exhaust device 21 having a vacuum pump (not shown) through an exhaust port 20a so that the inside thereof can be evacuated.
  • an ionizer 22 that ionizes the gas cluster by colliding electrons with the gas cluster in order from the partition wall 1 a side, and an electric field is applied to the gas cluster ion to accelerate toward the substrate S that is the object to be processed.
  • a plurality of electrodes 23A, 23B, 23C, 23D to be made and a Faraday cup 25 in which a holder 24 for holding the substrate S is accommodated are arranged.
  • the ionizer 22 has an electron supply source (not shown) that supplies electrons that collide with the gas cluster.
  • the ionizer 22 is maintained at a positive potential by an ionizer power supply 26.
  • a plurality of electrodes 23 A to 23 D installed between the ionizer 22 and the substrate S on the holder 24 are kept at a negative potential by an electrode power source 27.
  • the number of electrodes for applying an electric field to gas cluster ions is not limited to four.
  • the nozzle 12 is connected to an H 2 O supply source 32 that supplies high-pressure steam through a high-pressure gas supply pipe 31.
  • the high pressure gas supply pipe 31 is provided with an open / close valve 33.
  • the H 2 O cluster introduced into the irradiation unit 20 is ionized by the ionizer 22.
  • electrons are extracted from an electron source (not shown) and collided with the H 2 O cluster to ionize the cluster.
  • the ionizer 22 is maintained at a positive potential by the ionizer power source 26, and the electrodes 23 A to 23 D are set to a potential lower than the potential of the ionizer 22 by the electrode power source 27. Accordingly, positively charged H 2 O cluster ions ionized by collision with electrons are extracted by the plurality of electrodes 23A to 23D to which a voltage lower than that of the ionizer 22 is applied. That is, in order to extract the H 2 O cluster ion beam from the ionizer 22 and transport it to the substrate S, a potential difference of about several tens of kV is maintained between the ionizer 22 and the electrodes 23A to 23D.
  • the H 2 O cluster ions extracted from the ionizer 22 are accelerated by the electrodes 23A to 23D, and after the beam is focused and the cluster size is separated, the substrate S is irradiated. Since the gas cluster ion beam apparatus 100 that irradiates the ionized H 2 O cluster ions irradiates a large amount of ions with a small current, a high processing speed can be obtained, and the sheet-like graphene can be applied to the processing surface. It has the feature that there is little irradiation damage.
  • graphene is processed using the gas cluster ion beam apparatus 100 illustrated in FIG.
  • a condition for processing graphene using the gas cluster ion beam apparatus 100 shown in FIG. 1 it is preferable to adopt a condition that can suppress the kinetic energy per molecule to be low, for example, kinetic energy per molecule.
  • the condition that can be suppressed to 10 eV or less is more preferable.
  • H 2 O molecules or clusters in which H 2 O molecules are aggregated are ionized and accelerated and transported as an ion beam.
  • the graphene is irradiated with an ion beam controlled so that the kinetic energy per molecule is 10 eV or less.
  • H 2 O and graphene cause the following chemical reaction, and the graphene is etched.
  • the kinetic energy per molecule of the ion beam is suppressed to a low level, preferably 10 eV or less, so that the zigzag edge of the chemically active graphene reacts preferentially and is etched. .
  • a graphene in which a chemically stable armchair type edge is formed is obtained.
  • a band gap can be formed from graphene of a zero gap semiconductor.
  • FIG. 2A is a drawing schematically showing sheet-like graphene 200 to be processed in the present embodiment.
  • the zigzag end JE is cleaved by irradiating the sheet-like graphene 200 of FIG. 2A with an ion beam using the gas cluster ion beam apparatus 100.
  • the cleavage site is indicated by a broken line CC.
  • the graphene nanoribbon 201 of armchair edge AE as shown to FIG. 2B can be produced.
  • the gas cluster ion beam apparatus irradiates the ion beam formed by ionizing the water molecule or the cluster in which the water molecules are aggregated, whereby the zigzag edge J of the graphene is obtained. It is possible to selectively etch E.
  • a graphene nanoribbon having an armchair type edge shape and a large band gap can be efficiently manufactured.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Carbon And Carbon Compounds (AREA)

Abstract

Selon le procédé de l'invention, un gaz comprenant des molécules H2O (vapeur d'eau) est introduit dans une unité générant des agrégats par la buse (12) d'un dispositif de faisceau d'ions à agrégats de gaz (100). La vapeur d'eau introduite est agrégée par refroidissement par détente adiabatique, et des agrégats H2O en forme de faisceau sont formés. Les agrégats H2O, qui ont été introduits dans une unité d'irradiation (20), sont ionisés par un dispositif d'ionisation (22). Les agrégats H2O, qui ont été ionisés et positivement chargés, sont attirés par une pluralité d'électrodes (23A-23D) auxquelles une tension plus basse que celle du dispositif d'ionisation (22) est appliquée ; après accélération, focalisation des faisceaux, et séparation des tailles d'agrégats par les électrodes (23A-23D), un substrat (S) sur lequel une feuille de graphène a été formée est irradiée pour graver le graphène et obtenir des nanorubans ayant des bords en forme de fauteuil.
PCT/JP2013/058909 2012-04-05 2013-03-27 Procédé de traitement du graphène, procédé de production de nanorubans de graphène, et nanorubans de graphène ainsi obtenus WO2013150931A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020147026445A KR20150006417A (ko) 2012-04-05 2013-03-27 그래핀의 가공 방법, 그래핀 나노리본의 제조 방법 및 그래핀 나노리본
US14/390,402 US20150179451A1 (en) 2012-04-05 2013-03-27 Method for processing graphene, method for producing graphene nanoribbons, and graphene nanoribbons

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JP2012-086173 2012-04-05
JP2012086173A JP2013216510A (ja) 2012-04-05 2012-04-05 グラフェンの加工方法

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KR (1) KR20150006417A (fr)
TW (1) TW201348129A (fr)
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JP6196920B2 (ja) * 2014-03-06 2017-09-13 東京エレクトロン株式会社 グラフェン加工方法
JP2018127369A (ja) * 2017-02-06 2018-08-16 東京エレクトロン株式会社 グラフェンの異方性エッチング方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002356317A (ja) * 2001-03-27 2002-12-13 Osaka Gas Co Ltd グラファイトリボンおよびその製造方法
JP2006272076A (ja) * 2005-03-28 2006-10-12 Seinan Kogyo Kk イオンビームによる表面改質方法
WO2011016832A2 (fr) * 2009-08-07 2011-02-10 Guardian Industries Corp. Dispositif électronique comprenant une ou plusieurs couches à base de graphène, et/ou procédé de fabrication de ces couches

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JP3447492B2 (ja) * 1996-11-12 2003-09-16 日本電気株式会社 炭素材料とその製造方法
JP5545735B2 (ja) * 2010-07-20 2014-07-09 日本電信電話株式会社 磁気電気効果素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002356317A (ja) * 2001-03-27 2002-12-13 Osaka Gas Co Ltd グラファイトリボンおよびその製造方法
JP2006272076A (ja) * 2005-03-28 2006-10-12 Seinan Kogyo Kk イオンビームによる表面改質方法
WO2011016832A2 (fr) * 2009-08-07 2011-02-10 Guardian Industries Corp. Dispositif électronique comprenant une ou plusieurs couches à base de graphène, et/ou procédé de fabrication de ces couches

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JP2013216510A (ja) 2013-10-24
TW201348129A (zh) 2013-12-01
US20150179451A1 (en) 2015-06-25
KR20150006417A (ko) 2015-01-16

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